Crystal structure and Hirshfeld surface analysis of 2-amino-6-[(1-phenyl­eth­yl)amino]-4-(thio­phen-2-yl)pyridine-3,5-dicarbo­nitrile

Naghiyev, F.N.; Khrustalev, V.N.; Asadov, K.A.; Akkurt, M.; Khalilov, A.N.; Bhattarai, A.; Mamedov, İ.G.

doi:10.1107/S2056989023003845

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 6| June 2023| Pages 526-530

https://doi.org/10.1107/S2056989023003845

Open

access

Crystal structure and Hirshfeld surface analysis of 2-amino-6-[(1-phenylethyl)amino]-4-(thiophen-2-yl)pyridine-3,5-dicarbonitrile

Farid N. Naghiyev,^a Victor N. Khrustalev,^b,^c Khammed A. Asadov,^a Mehmet Akkurt,^d Ali N. Khalilov,^e,^a Ajaya Bhattarai ^f ^* and İbrahim G. Mamedov ^a

^aDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148, Baku, Azerbaijan, ^bPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation, ^cN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, ^e"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), H. Aliyev str. 135, Az 1063, Baku, Azerbaijan, and ^fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 26 April 2023; accepted 28 April 2023; online 5 May 2023)

In the title compound, C₁₉H₁₅N₅S, the thiophene ring is disordered in a 0.6:0.4 ratio by an approximate 180° rotation of the ring around the C—C bond linking it to the pyridine ring. In the crystal, the molecules are linked by N—H⋯N hydrogen bonds into dimers with an R²₂(12) motif, forming chains along the b-axis direction. These chains are connected to each other by further N—H⋯N hydrogen bonds, forming a three-dimensional network. Furthermore, N—H⋯π and π–π [centroid–centroid separations = 3.899 (8) and 3.7938 (12) Å] interactions also contribute to the crystal cohesion. A Hirshfeld surface analysis indicated that the most important contributions to the surface contacts are from H⋯H (46.1%), N⋯H/H⋯N (20.4%) and C⋯H/H⋯C (17.4%) interactions.

Keywords: crystal structure; pyridine ring; thiophene ring; disorder; Hirshfeld surface analysis.

CCDC reference: 2260011

1. Chemical context

Diverse C—C, C—N and C—O bond-formation methods play important roles in organic synthesis. The reaction scopes have also been greatly expanded, employing these methods in different fields of chemistry, in both academia and industry (Çelik et al., 2023 ; Chalkha et al., 2023 ; Tapera et al., 2022 ; Gurbanov et al., 2020 ; Zubkov et al., 2018 ). The pyridine moiety is a widespread structural motif that can be found in various natural products and pharmacologically active compounds. 3,5-Dicyanopyridines have been reported as intermediates in the synthesis of pyrido[2,3-d]pyrimidines, pyridothienotriazines, azabenzanthracenes and pyrimidine S-nucleoside derivatives with a broad spectrum of biological activity (Cocco et al., 2005 ; Zhang et al., 2022 ; Poustforoosh et al., 2022 ). The design of new 3,5-dicyanopyridine derivatives is thus of great interest.

Continuing our studies of pyridine derivatives exhibiting biological activity, we designed and synthesized a novel 3,5-dicyanopyridine in this series. Thus, in the framework of our ongoing structural studies (Naghiyev et al., 2020 , 2021 , 2022 ), we report the crystal structure and Hirshfeld surface analysis of the title compound, 2-amino-6-[(1-phenylethyl)amino]-4-(thiophen-2-yl)pyridine-3,5-dicarbonitrile.

2. Structural commentary

The pyridine ring (N1/C2–C6) of the title compound (Fig. 1) is largely planar [maximum deviation = 0.015 (2) Å for C5]. The thiophene and 1-phenylethan-1-amine groups are linked to the central pyridine ring in an equatorial arrangement. The major and minor parts (S1/C15–C18 and S1A/C15A–C18A) of the disordered thiophene ring make dihedral angles of 44.8 (5) and 48.9 (6)°, respectively, with the pyridine ring. The dihedral angle between the phenyl (C7–C12) and pyridine (N1/C2–C6) rings is 64.42 (11) °.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level. For clarity, the minor disorder component is not shown.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the molecules are linked by N—H⋯N hydrogen bonds into dimers with an $[R_{2}^{2}]$ (12) motif (Bernstein et al., 1995 ; Table 1, Fig. 2), forming chains along the b-axis direction. These chains are connected to each other by further N—H⋯N hydrogen bonds, forming a three-dimensional network (Tables 1 and 2, Figs. 3 and 4). Furthermore, N—H⋯π and π–π interactions [Cg1⋯Cg1ⁱ = 3.899 (8) Å; slippage = 1.899 Å; Cg3⋯Cg3ⁱⁱ = 3.7938 (12) Å; slippage = 1.383 Å; symmetry codes: (i) −x, 1 − y, z; (ii) 1 − x, 1 − y, z; Cg1 and Cg3 are the centroids of the major component of the disordered thiophene ring and of the pyridine ring, respectively] also contribute to crystal cohesion (Figs. 5 and 6).

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N19ⁱ	0.91 (3)	2.28 (3)	3.152 (3)	163 (3)
N6—H6B⋯N14ⁱⁱ	0.89 (3)	2.17 (4)	3.033 (3)	164 (3)
N6—H6A⋯Cg4ⁱⁱⁱ	0.91 (3)	2.62 (4)	3.405 (2)	145 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+1]$ ; (iii) .

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H13A⋯H6A	2.36	−x, 1 − y, z
H6B⋯N14	2.18	$[{1\over 2}]$ − x, $[{1\over 2}]$ + y, 1 − z
H16⋯N19	2.56	1 − x, 1 − y, z
C17⋯H9	2.86	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z
C10⋯C13	3.58	1 + x, y, z
H12⋯H18A	2.31	x, y, 1 + z
H18⋯H11	2.34	1 − x, 1 − y, −1 + z

Figure 2
View of the molecular packing along the a axis. N—H⋯N hydrogen bonds are shown as dashed lines. For clarity, the minor disorder component is not shown.

Figure 3
View of the molecular packing along the b axis. Hydrogen bonds are shown as dashed lines.

Figure 4
View of the molecular packing along the c axis. Hydrogen bonds are shown as dashed lines.

Figure 5
View of the molecular packing along the b axis. N—H⋯π interactions and π–π stacking interactions are shown as dashed lines.

Figure 6
View of the molecular packing along the c axis. N—H⋯π interactions and π–π stacking interactions are shown as dashed lines.

Crystal Explorer 17.5 (Spackman et al., 2021 ) was used to generate Hirshfeld surfaces and two-dimensional fingerprint plots in order to quantify the intermolecular interactions in the crystal. The intermolecular interactions are depicted as red spots, which denotes the N—H⋯N hydrogen bonds, on the Hirshfeld surface mapped over d_norm in the range −0.4485 to +1.5784 a.u. (Fig. 7a,b). Fig. 8 shows the two-dimensional fingerprint plots. The H⋯H contacts comprise 46.1% of the total interactions. Besides this contact, N⋯H/H⋯N (20.4%) and C⋯H/H⋯C (17.4%) interactions make significant contributions to the total Hirshfeld surface. The percentage contributions of the C⋯C, N⋯C/C⋯N, N⋯N, S⋯C/C⋯S, S⋯H/H⋯S and S⋯S contacts are 6.9, 3.8, 2.7, 1.5, 0.6 and 0.6%, respectively.

Figure 7
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm, with a fixed colour scale of −0.4485 to +1.5784 a.u. N—H⋯N hydrogen bonds are shown as dashed lines.

Figure 8
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) N⋯H/H⋯N and (d) C⋯H/H⋯C interactions. [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

4. Database survey

The four related compounds found as a result of the search for `2,6-diamino-4-(thiophen-2-yl)pyridine-3,5-dicarbonitrile' in the Cambridge Structure Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) are MUCLAA (Vu Quoc et al., 2019 ), WOJCIJ (Vishnupriya et al., 2014a ), WOPLAQ (Vishnupriya et al., 2014b ) and DOPWOW (Vishnupriya et al., 2014c ).

In the crystal of MUCLAA (space group P2₁/c), chains running along the b-axis direction are formed through N—H⋯O interactions between the 1,4-dihydropyridine N atom and one of the O atoms of the ester groups. Neighbouring chains are linked by C—H⋯O and C—H⋯π interactions. In the crystal of WOJCIJ (space group P2₁/c), inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate $[R_{2}^{2}]$ (16) loops and the dimers are linked by C—H⋯π and aromatic π–π stacking interactions into a three-dimensional network. In WOPLAQ (space group P2₁/n), inversion dimers linked by pairs of N—H⋯N_c (c = cyanide) hydrogen bonds generate $[R_{2}^{2}]$ (16) loops. In DOPWOW (space group Pbca), inversion dimers linked by pairs of N—H⋯N_n (n = nitrile) hydrogen bonds generate $[R_{2}^{2}]$ (16) loops. Aromatic π–π stacking and very weak C—H⋯π interactions are also observed.

5. Synthesis and crystallization

To a solution of 2-(thiophen-2-ylmethylene)malononitrile (0.82 g; 5.1 mmol) and malononitrile (0.34 g; 5.2 mmol) in methanol (25 mL), phenylethylamine (0.63 g; 5.2 mmol) was added and the mixture was stirred at room temperature for 48 h. Then 15 mL of methanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from ethanol/water (1:1) solution (yield 94%; m.p. 460–461 K).

¹H NMR (300 MHz, DMSO-d₆, ppm): 1.55 (d, 3H, CH₃, ³J_H–H = 7 MHz); 5.45 (k, 1H, CH—Ar, ³J_H–H =7,1 MHz); 7.21–7.88 (m, 11H, 5CH_arom + 3CH_thienyl + NH₂ + NH); ¹³C NMR (75 MHz, DMSO-d₆, ppm): 21.69 (CH₃), 50.00 (CH—Ar), 79.77 (=C_tert), 80.92 (=C_tert), 116.85 (CN), 116.97 (CN), 127.14 (2CH_arom), 127.22 (CH_arom), 128.11 (CH_thienyl), 128.63 (2CH_arom), 130.14 (CH_thienyl), 130.75 (CH_thienyl), 134.53 (C_ar), 144.53 (C_thienyl), 152.30 (=C_tert), 158.70 (N=C_tert), 161.38 (=C_tert).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The thiophene ring in the title compound was modelled as disordered over two sets of sites related by an approximate rotation of 180° about the C4—C15 bond in a 0.6:0.4 ratio. EADP commands in SHELXL were used for the U_ij values of equivalent atom pairs (e.g., C16 and C16A) and DFIX commands were used to restrain the nearest-neighbour and next-nearest-neighbour bond distances in the two disorder components to be equal with a standard deviation of 0.03 Å. All C-bound H atoms were placed in calculated positions (0.95–1.00 Å) and refined as riding with U_iso(H) = 1.2 or 1.5U_eq(C). The N-bound H atoms were located in a difference map and refined with U_iso(H) = 1.2U_eq(N) [N2—H2 = 0.91 (3) Å, N6—H6A = 0.91 (3) Å, N6—H6B = 0.89 (3) Å].

Table 3
Experimental details

Crystal data
Chemical formula	C₁₉H₁₅N₅S
M_r	345.42
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	100
a, b, c (Å)	7.89079 (13), 16.4990 (3), 13.1394 (3)
V (Å³)	1710.62 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.77
Crystal size (mm)	0.40 × 0.04 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.532, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	26907, 3713, 3612
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.05
No. of reflections	3713
No. of parameters	276
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.25
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.13 (3)
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2260011

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989023003845/vm2282sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023003845/vm2282Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023003845/vm2282Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2022); cell refinement: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2022); data reduction: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

2-Amino-6-[(1-phenylethyl)amino]-4-(thiophen-2-yl)pyridine-3,5-dicarbonitrile top

Crystal data top

C₁₉H₁₅N₅S	D_x = 1.341 Mg m⁻³
M_r = 345.42	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2	Cell parameters from 17132 reflections
a = 7.89079 (13) Å	θ = 3.4–79.2°
b = 16.4990 (3) Å	µ = 1.77 mm⁻¹
c = 13.1394 (3) Å	T = 100 K
V = 1710.62 (6) Å³	Needle, colourless
Z = 4	0.40 × 0.04 × 0.03 mm
F(000) = 720

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3612 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.044
φ and ω scans	θ_max = 79.7°, θ_min = 3.4°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2022)	h = −10→9
T_min = 0.532, T_max = 0.939	k = −21→20
26907 measured reflections	l = −16→16
3713 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0507P)² + 0.5356P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3713 reflections	Δρ_max = 0.15 e Å⁻³
276 parameters	Δρ_min = −0.25 e Å⁻³
12 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: difference Fourier map	Absolute structure parameter: 0.13 (3)

Special details top

Experimental. CrysAlisPro 1.171.41.123a (Rigaku OD, 2022); Numerical absorption correction based on Gaussian integration over a multifaceted crystal model; Empirical absorption correction using spherical harmonics implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.1793 (3)	0.56636 (9)	0.24471 (14)	0.0306 (3)	0.6
S1A	0.3236 (6)	0.42012 (16)	0.2521 (3)	0.0254 (6)	0.4
N1	0.2686 (2)	0.50614 (12)	0.64994 (15)	0.0250 (4)
C1	0.1399 (3)	0.38542 (14)	0.77369 (17)	0.0270 (5)
H1	0.1288	0.4439	0.7928	0.032*
C2	0.2054 (3)	0.44038 (13)	0.60337 (17)	0.0239 (4)
N2	0.1451 (2)	0.38039 (12)	0.66239 (15)	0.0263 (4)
H2	0.112 (4)	0.332 (2)	0.636 (2)	0.032*
C3	0.1980 (3)	0.43395 (13)	0.49462 (17)	0.0237 (4)
C4	0.2528 (2)	0.49903 (13)	0.43479 (15)	0.0236 (4)
C5	0.3127 (3)	0.56866 (13)	0.48450 (17)	0.0244 (4)
C6	0.3206 (3)	0.56878 (12)	0.59318 (17)	0.0242 (4)
N6	0.3851 (3)	0.63253 (13)	0.64322 (17)	0.0288 (4)
H6A	0.392 (4)	0.6297 (19)	0.712 (3)	0.035*
H6B	0.413 (4)	0.679 (2)	0.615 (2)	0.035*
C7	0.2992 (3)	0.35278 (14)	0.82352 (17)	0.0255 (4)
C8	0.3550 (3)	0.27466 (15)	0.80460 (19)	0.0313 (5)
H8	0.2958	0.2417	0.7571	0.038*
C9	0.4974 (3)	0.24370 (16)	0.8545 (2)	0.0352 (5)
H9	0.5354	0.1903	0.8402	0.042*
C10	0.5827 (3)	0.29053 (17)	0.9245 (2)	0.0352 (5)
H10	0.6777	0.2691	0.9599	0.042*
C11	0.5292 (3)	0.3690 (2)	0.9429 (2)	0.0429 (6)
H11	0.5883	0.4019	0.9904	0.051*
C12	0.3887 (3)	0.39989 (17)	0.8918 (2)	0.0361 (6)
H12	0.3540	0.4541	0.9041	0.043*
C13	−0.0172 (3)	0.34112 (18)	0.8124 (2)	0.0361 (6)
H13A	−0.1190	0.3670	0.7847	0.054*
H13B	−0.0203	0.3435	0.8869	0.054*
H13C	−0.0133	0.2844	0.7904	0.054*
C14	0.1206 (3)	0.36403 (14)	0.45060 (17)	0.0257 (4)
N14	0.0540 (3)	0.30718 (12)	0.41871 (16)	0.0310 (4)
C15	0.251 (3)	0.4906 (6)	0.3229 (3)	0.029 (3)	0.6
C16	0.3006 (16)	0.4236 (4)	0.2681 (5)	0.025 (2)	0.6
H16	0.3422	0.3748	0.2974	0.030*	0.6
C17	0.2816 (10)	0.4371 (4)	0.1618 (5)	0.0346 (15)	0.6
H17	0.3135	0.3981	0.1121	0.042*	0.6
C18	0.2137 (10)	0.5107 (4)	0.1371 (5)	0.0366 (17)	0.6
H18	0.1893	0.5284	0.0698	0.044*	0.6
C15A	0.246 (4)	0.4989 (10)	0.3229 (3)	0.024 (4)	0.4
C16A	0.180 (2)	0.5595 (5)	0.2643 (5)	0.025 (2)	0.4
H16A	0.1294	0.6078	0.2899	0.030*	0.4
C17A	0.1963 (15)	0.5398 (6)	0.1596 (6)	0.029 (2)	0.4
H17A	0.1595	0.5750	0.1069	0.035*	0.4
C18A	0.2696 (14)	0.4661 (7)	0.1404 (6)	0.032 (2)	0.4
H18A	0.2877	0.4439	0.0746	0.038*	0.4
C19	0.3707 (3)	0.63853 (14)	0.43145 (18)	0.0256 (4)
N19	0.4186 (3)	0.69712 (13)	0.39337 (16)	0.0298 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0317 (6)	0.0288 (5)	0.0314 (6)	−0.0050 (5)	−0.0049 (7)	0.0067 (5)
S1A	0.0253 (13)	0.0248 (10)	0.0261 (9)	0.0020 (6)	0.0027 (10)	−0.0027 (8)
N1	0.0238 (8)	0.0243 (9)	0.0269 (9)	−0.0001 (7)	−0.0007 (7)	−0.0006 (7)
C1	0.0261 (10)	0.0271 (10)	0.0279 (11)	0.0024 (8)	0.0027 (9)	−0.0004 (8)
C2	0.0183 (9)	0.0223 (9)	0.0311 (11)	0.0022 (8)	0.0001 (8)	0.0025 (8)
N2	0.0276 (9)	0.0248 (9)	0.0266 (9)	−0.0007 (7)	0.0000 (7)	0.0024 (7)
C3	0.0199 (9)	0.0236 (10)	0.0276 (10)	0.0018 (9)	−0.0015 (8)	0.0009 (8)
C4	0.0157 (9)	0.0249 (11)	0.0303 (11)	0.0022 (8)	−0.0005 (7)	0.0013 (9)
C5	0.0190 (9)	0.0246 (10)	0.0298 (10)	0.0012 (9)	0.0002 (8)	0.0012 (8)
C6	0.0190 (9)	0.0221 (10)	0.0314 (11)	0.0014 (8)	−0.0005 (8)	−0.0016 (8)
N6	0.0314 (9)	0.0257 (10)	0.0293 (10)	−0.0028 (8)	−0.0022 (8)	−0.0013 (8)
C7	0.0234 (10)	0.0289 (11)	0.0242 (9)	−0.0018 (8)	0.0052 (8)	0.0007 (8)
C8	0.0296 (11)	0.0290 (11)	0.0355 (12)	−0.0022 (9)	−0.0070 (9)	−0.0009 (9)
C9	0.0301 (11)	0.0311 (12)	0.0443 (13)	0.0014 (10)	−0.0047 (11)	0.0011 (11)
C10	0.0246 (10)	0.0491 (15)	0.0319 (11)	−0.0009 (10)	−0.0018 (9)	0.0025 (11)
C11	0.0339 (13)	0.0532 (16)	0.0415 (14)	−0.0033 (12)	−0.0083 (11)	−0.0148 (13)
C12	0.0335 (12)	0.0384 (14)	0.0364 (12)	0.0008 (10)	−0.0007 (10)	−0.0108 (11)
C13	0.0260 (11)	0.0479 (15)	0.0344 (12)	0.0015 (11)	0.0037 (10)	0.0083 (11)
C14	0.0245 (9)	0.0252 (10)	0.0273 (10)	0.0023 (8)	−0.0004 (8)	0.0028 (9)
N14	0.0334 (10)	0.0264 (10)	0.0331 (10)	−0.0023 (8)	−0.0034 (8)	0.0012 (8)
C15	0.022 (6)	0.027 (4)	0.036 (6)	−0.011 (3)	−0.004 (4)	0.009 (3)
C16	0.023 (3)	0.033 (3)	0.020 (3)	0.0021 (19)	0.003 (2)	−0.0031 (17)
C17	0.027 (3)	0.049 (4)	0.028 (3)	−0.006 (3)	−0.001 (2)	−0.003 (3)
C18	0.029 (3)	0.061 (6)	0.020 (3)	−0.016 (4)	0.001 (3)	0.004 (3)
C15A	0.017 (7)	0.036 (6)	0.020 (6)	0.001 (6)	0.004 (6)	−0.005 (5)
C16A	0.023 (3)	0.033 (3)	0.020 (3)	0.0021 (19)	0.003 (2)	−0.0031 (17)
C17A	0.027 (3)	0.048 (6)	0.012 (4)	0.000 (4)	0.003 (3)	−0.001 (3)
C18A	0.022 (4)	0.053 (8)	0.020 (4)	0.011 (5)	−0.001 (3)	0.005 (5)
C19	0.0224 (9)	0.0251 (10)	0.0293 (10)	0.0005 (8)	−0.0009 (9)	−0.0030 (9)
N19	0.0300 (9)	0.0265 (10)	0.0331 (10)	−0.0034 (8)	0.0004 (8)	−0.0006 (8)

Geometric parameters (Å, º) top

S1—C18	1.708 (4)	C8—H8	0.9500
S1—C15	1.713 (4)	C9—C10	1.377 (4)
S1A—C18A	1.707 (4)	C9—H9	0.9500
S1A—C15A	1.711 (4)	C10—C11	1.384 (4)
N1—C6	1.339 (3)	C10—H10	0.9500
N1—C2	1.342 (3)	C11—C12	1.392 (4)
C1—N2	1.465 (3)	C11—H11	0.9500
C1—C7	1.516 (3)	C12—H12	0.9500
C1—C13	1.526 (3)	C13—H13A	0.9800
C1—H1	1.0000	C13—H13B	0.9800
C2—N2	1.344 (3)	C13—H13C	0.9800
C2—C3	1.434 (3)	C14—N14	1.154 (3)
N2—H2	0.91 (3)	C15—C16	1.377 (4)
C3—C4	1.399 (3)	C16—C17	1.423 (4)
C3—C14	1.428 (3)	C16—H16	0.9500
C4—C5	1.404 (3)	C17—C18	1.368 (9)
C4—C15A	1.472 (4)	C17—H17	0.9500
C4—C15	1.477 (3)	C18—H18	0.9500
C5—C19	1.423 (3)	C15A—C16A	1.368 (4)
C5—C6	1.429 (3)	C16A—C17A	1.420 (4)
C6—N6	1.341 (3)	C16A—H16A	0.9500
N6—H6A	0.91 (3)	C17A—C18A	1.369 (13)
N6—H6B	0.89 (3)	C17A—H17A	0.9500
C7—C12	1.382 (3)	C18A—H18A	0.9500
C7—C8	1.384 (3)	C19—N19	1.152 (3)
C8—C9	1.398 (3)

C18—S1—C15	93.0 (4)	C9—C10—C11	119.5 (2)
C18A—S1A—C15A	92.3 (5)	C9—C10—H10	120.2
C6—N1—C2	118.95 (19)	C11—C10—H10	120.2
N2—C1—C7	112.82 (18)	C10—C11—C12	120.1 (2)
N2—C1—C13	109.13 (19)	C10—C11—H11	119.9
C7—C1—C13	111.07 (19)	C12—C11—H11	119.9
N2—C1—H1	107.9	C7—C12—C11	121.0 (3)
C7—C1—H1	107.9	C7—C12—H12	119.5
C13—C1—H1	107.9	C11—C12—H12	119.5
N1—C2—N2	117.6 (2)	C1—C13—H13A	109.5
N1—C2—C3	122.0 (2)	C1—C13—H13B	109.5
N2—C2—C3	120.4 (2)	H13A—C13—H13B	109.5
C2—N2—C1	122.9 (2)	C1—C13—H13C	109.5
C2—N2—H2	122 (2)	H13A—C13—H13C	109.5
C1—N2—H2	115 (2)	H13B—C13—H13C	109.5
C4—C3—C14	121.65 (19)	N14—C14—C3	177.1 (2)
C4—C3—C2	119.4 (2)	C16—C15—C4	126.3 (4)
C14—C3—C2	118.7 (2)	C16—C15—S1	111.5 (3)
C3—C4—C5	118.08 (19)	C4—C15—S1	122.2 (3)
C3—C4—C15A	123.3 (11)	C15—C16—C17	110.9 (5)
C5—C4—C15A	118.6 (11)	C15—C16—H16	124.5
C3—C4—C15	118.9 (7)	C17—C16—H16	124.5
C5—C4—C15	123.0 (7)	C18—C17—C16	114.4 (6)
C4—C5—C19	122.9 (2)	C18—C17—H17	122.8
C4—C5—C6	118.7 (2)	C16—C17—H17	122.8
C19—C5—C6	118.3 (2)	C17—C18—S1	110.1 (6)
N1—C6—N6	116.7 (2)	C17—C18—H18	125.0
N1—C6—C5	122.8 (2)	S1—C18—H18	125.0
N6—C6—C5	120.5 (2)	C16A—C15A—C4	125.1 (5)
C6—N6—H6A	118 (2)	C16A—C15A—S1A	112.8 (3)
C6—N6—H6B	125 (2)	C4—C15A—S1A	122.1 (4)
H6A—N6—H6B	117 (3)	C15A—C16A—C17A	109.9 (6)
C12—C7—C8	118.5 (2)	C15A—C16A—H16A	125.0
C12—C7—C1	120.3 (2)	C17A—C16A—H16A	125.0
C8—C7—C1	121.1 (2)	C18A—C17A—C16A	115.0 (9)
C7—C8—C9	120.8 (2)	C18A—C17A—H17A	122.5
C7—C8—H8	119.6	C16A—C17A—H17A	122.5
C9—C8—H8	119.6	C17A—C18A—S1A	110.0 (8)
C10—C9—C8	120.1 (2)	C17A—C18A—H18A	125.0
C10—C9—H9	120.0	S1A—C18A—H18A	125.0
C8—C9—H9	120.0	N19—C19—C5	176.4 (2)

C6—N1—C2—N2	−176.22 (19)	C1—C7—C8—C9	−176.9 (2)
C6—N1—C2—C3	2.5 (3)	C7—C8—C9—C10	0.9 (4)
N1—C2—N2—C1	2.4 (3)	C8—C9—C10—C11	−1.7 (4)
C3—C2—N2—C1	−176.30 (19)	C9—C10—C11—C12	0.8 (4)
C7—C1—N2—C2	−90.5 (2)	C8—C7—C12—C11	−1.8 (4)
C13—C1—N2—C2	145.6 (2)	C1—C7—C12—C11	176.0 (2)
N1—C2—C3—C4	−2.2 (3)	C10—C11—C12—C7	1.0 (4)
N2—C2—C3—C4	176.47 (18)	C3—C4—C15—C16	−42 (2)
N1—C2—C3—C14	−176.64 (19)	C5—C4—C15—C16	135.4 (17)
N2—C2—C3—C14	2.0 (3)	C15A—C4—C15—C16	173 (27)
C14—C3—C4—C5	174.0 (2)	C3—C4—C15—S1	136.5 (12)
C2—C3—C4—C5	−0.3 (3)	C5—C4—C15—S1	−46 (2)
C14—C3—C4—C15A	−4.1 (12)	C15A—C4—C15—S1	−8 (23)
C2—C3—C4—C15A	−178.4 (11)	C18—S1—C15—C16	0.1 (16)
C14—C3—C4—C15	−8.0 (9)	C18—S1—C15—C4	−179.0 (17)
C2—C3—C4—C15	177.7 (8)	C4—C15—C16—C17	−179.8 (17)
C3—C4—C5—C19	−179.6 (2)	S1—C15—C16—C17	1 (2)
C15A—C4—C5—C19	−1.4 (11)	C15—C16—C17—C18	−2.2 (17)
C15—C4—C5—C19	2.4 (9)	C16—C17—C18—S1	2.3 (10)
C3—C4—C5—C6	2.2 (3)	C15—S1—C18—C17	−1.3 (10)
C15A—C4—C5—C6	−179.5 (11)	C3—C4—C15A—C16A	130 (2)
C15—C4—C5—C6	−175.7 (8)	C5—C4—C15A—C16A	−48 (4)
C2—N1—C6—N6	−179.01 (19)	C15—C4—C15A—C16A	168 (28)
C2—N1—C6—C5	−0.4 (3)	C3—C4—C15A—S1A	−50 (3)
C4—C5—C6—N1	−2.0 (3)	C5—C4—C15A—S1A	132.2 (18)
C19—C5—C6—N1	179.74 (19)	C15—C4—C15A—S1A	−12 (23)
C4—C5—C6—N6	176.58 (19)	C18A—S1A—C15A—C16A	0 (2)
C19—C5—C6—N6	−1.6 (3)	C18A—S1A—C15A—C4	−180 (2)
N2—C1—C7—C12	126.2 (2)	C4—C15A—C16A—C17A	179 (2)
C13—C1—C7—C12	−110.9 (3)	S1A—C15A—C16A—C17A	−1 (3)
N2—C1—C7—C8	−56.0 (3)	C15A—C16A—C17A—C18A	1 (2)
C13—C1—C7—C8	66.9 (3)	C16A—C17A—C18A—S1A	−1.2 (15)
C12—C7—C8—C9	0.9 (4)	C15A—S1A—C18A—C17A	0.6 (15)

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N19ⁱ	0.91 (3)	2.28 (3)	3.152 (3)	163 (3)
N6—H6B···N14ⁱⁱ	0.89 (3)	2.17 (4)	3.033 (3)	164 (3)
N6—H6A···Cg4ⁱⁱⁱ	0.91 (3)	2.62 (4)	3.405 (2)	145 (3)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1; (ii) −x+1/2, y+1/2, −z+1; (iii) −x+1, −y+1, z.

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
H13A···H6A	2.36	-x, 1 - y, z
H6B···N14	2.18	1/2 - x, 1/2 + y, 1 - z
H16···N19	2.56	1 - x, 1 - y, z
C17···H9	2.86	-1/2 + x, 1/2 - y, 1 - z
C10···C13	3.58	1 + x, y, z
H12···H18A	2.31	x, y, 1 + z
H18···H11	2.34	1 - x, 1 - y, -1 + z

Acknowledgements

Authors' contributions are as follows. Conceptualization, ANK and IGM; methodology, ANK, FNN and IGM; investigation, ANK, MA and KAA; writing (original draft), MA and ANK; writing (review and editing of the manuscript), MA and ANK; visualization, MA, ANK and IGM; funding acquisition, VNK, AB and ANK; resources, AB, VNK and KAA; supervision, ANK and MA.

Funding information

This paper was supported by Baku State University and the RUDN University Strategic Academic Leadership Program.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Çelik, M. S., Çetinus, A., Yenidünya, A. F., Çetinkaya, S. & Tüzün, B. (2023). J. Mol. Struct. 1272, 134158. Google Scholar
Chalkha, M., Ameziane el Hassani, A., Nakkabi, A., Tüzün, B., Bakhouch, M., Benjelloun, A. T., Sfaira, M., Saadi, M., Ammari, L. E. & Yazidi, M. E. (2023). J. Mol. Struct. 1273, 134255. Web of Science CSD CrossRef Google Scholar
Cocco, M. T., Congiu, C., Lilliu, V. & Onnis, V. (2005). Eur. J. Med. Chem. 40, 1365–1372. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020). Chem. Eur. J. 26, 14833–14837. Web of Science CSD CrossRef CAS PubMed Google Scholar
Naghiyev, F. N., Akkurt, M., Askerov, R. K., Mamedov, I. G., Rzayev, R. M., Chyrka, T. & Maharramov, A. M. (2020). Acta Cryst. E76, 720–723. Web of Science CSD CrossRef IUCr Journals Google Scholar
Naghiyev, F. N., Khrustalev, V. N., Novikov, A. P., Akkurt, M., Rzayev, R. M., Akobirshoeva, A. A. & Mamedov, I. G. (2022). Acta Cryst. E78, 554–558. Web of Science CSD CrossRef IUCr Journals Google Scholar
Naghiyev, F. N., Tereshina, T. A., Khrustalev, V. N., Akkurt, M., Rzayev, R. M., Akobirshoeva, A. A. & Mamedov, İ. G. (2021). Acta Cryst. E77, 516–521. Web of Science CSD CrossRef IUCr Journals Google Scholar
Poustforoosh, A., Hashemipour, H., Tüzün, B., Azadpour, M., Faramarz, S., Pardakhty, A., Mehrabani, M. & Nematollahi, M. H. (2022). Curr. Microbiol. 79, 241. Web of Science CrossRef PubMed Google Scholar
Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Tapera, M., Kekeçmuhammed, H., Tüzün, B., Sarıpınar, E., Koçyiğit, M., Yıldırım, E., Doğan, M. & Zorlu, Y. (2022). J. Mol. Struct. 1269, 133816. Web of Science CSD CrossRef Google Scholar
Vishnupriya, R., Suresh, J., Bharkavi, S., Perumal, S. & Lakshman, P. L. N. (2014a). Acta Cryst. E70, o968–o969. CSD CrossRef IUCr Journals Google Scholar
Vishnupriya, R., Suresh, J., Gunasekaran, P., Perumal, S. & Lakshman, P. L. N. (2014b). Acta Cryst. E70, o978. CSD CrossRef IUCr Journals Google Scholar
Vishnupriya, R., Suresh, J., Sakthi, M., Perumal, S. & Lakshman, P. L. N. (2014c). Acta Cryst. E70, o1120–o1121. CSD CrossRef IUCr Journals Google Scholar
Vu Quoc, T., Tran Thi Thuy, D., Phung Ngoc, T., Vu Quoc, M., Nguyen, H., Duong Khanh, L., Tu Quang, A. & Van Meervelt, L. (2019). Acta Cryst. E75, 1861–1865. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, X., Tao, F., Cui, T., Luo, C., Zhou, Z., Huang, Y., Tan, L., Peng, W. & Wu, C. (2022). Molecules, 27, 7187. Web of Science CrossRef PubMed Google Scholar
Zubkov, F. I., Mertsalov, D. F., Zaytsev, V. P., Varlamov, A. V., Gurbanov, A. V., Dorovatovskii, P. V., Timofeeva, T. V., Khrustalev, V. N. & Mahmudov, K. T. (2018). J. Mol. Liq. 249, 949–952. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.